Light-sensitive diazotype material



United StatesPateiit LIGHT-SENSITIV E DIAZOTYPE MATERIAL Oskar Siis,Wiesbaden-Biebrich, and Manfred Grundkiitter, Wieshaden, Germany,assignors, by mesne assignments, to Keutfel & Esser Co., Hoboken, N. 1.,a corporation of New Jersey No Drawing. Application August 6, 1954Serial No. 448,393

Claims priority, application Germany August 11, 1953 12 Claims. (CI.96-91) This invention is concerned with light-sensitive diazotypematerial. It is particularly advantageous when applied to diazotypematerials of the one component or moist developing type.

Diazo compounds derived from para-phenylene diamine in which thenon-cliazotized amino group is secondary or tertiary have been used forthe production of a lightsensitive layer on base material suitable fordiazotype printing. Diazo compounds derived from para-phenylene diamineand having alkyl residues with external atom groups at the nitrogen ofthe un-diazotized amino group, e. g. substituted amino groups orhydroxyl groups etherified by aliphatic hydrocarbon residues, aredescribed for this purpose in German patent specification No. 831,804and U. S. Patent No. 2,336,309. On account of their low couplingactivity, diazo compounds of this type are used particularly for theproduction of so-called two-component diazotype layers for drydevelopment.

An object of the present invention is to provide an improvedlight-sensitive diazotype material particularly for one component .ormoist development.

The improved diazotype materials according to the present inventionprovide light sensitive diazotype material in which the light-sensitivelayer includes a diazo compound of para-phenylene diamine of the generalformula:

wherein -Ph is a phenylene residue which may be substituted 7 when thediazo compounds. of acylated p-phenylene1diamines were used as thelight-sensitivesubstance.

By introducing substitutents into R e. g. halogen atoms, or by enlargingthis residue, the coupling process during development can frequently beaccelerated.

by the diazo compounds of this invention. The com pounds are preferablyapplied in the form of water-soluble phloroglucinol and resorcinol areparticplarly suitable.

NJ The shade of color can also be affected by introducing substituentsinto the phenylene residue which carries the diazo group. Positivesubstituents generally cause a lightening of the tone. Diazo compoundsof this nature are suitable for the production of intermediate originalsof good opacity for ultraviolet light.

The ligh-sensitive layers may contain the usual stabilizers in the formof inorganic or organic acids, acid salts and salts of aromaticsulphonic acids. Anti-yellowing materials, particularly thiourea and itswater-soluble derivatives may also be present in the layers to improvethe background of the copies after development. The light-sensitivematerial may be further improved to produce copies with increasedcontrast by incorporating suspensions of finely-divided silicon dioxideor of silicates of alkaline earth metals in the sensitizing solutions.

Known methods are used to produce the diazo compounds of this invention.For example, monoalkylated amines are used as starting material and, arecaused to react with the toluene-sulphonic acid esters of glycol--monoaryl-ethers or the aryl ethers of ethylene chlorhydrin or ethylenebromhydrin. The aryloxy alkylated amino benzenes thus obtained areconverted to azo dyes by coupling with ,diazotized sulphanilic acid ordiazotized aniline, and from these the corresponding phenylene diaminescan be obtained by reduction and can be converted in'the usual manner tothe diazo compounds. The amino group can also be introduced bynitrosating the tertiary bases and reducing the nitroso compounds.

The sulphur analogues are obtainable in a similar manner. in this casethe thioaryl ethers of thiochlorhydrins are used as starting materialsfor reaction with the secondary bases.

The following is a description by way of example of methods of carryingthe invention into efiect. The formulae referred to are tabulated belowthe examples.

Example I A raw paper base material suitable for the production ofphoto-copying material is coated with this solution in normal manner andafter drying is exposed under a transparent drawing original. Theexposed paper is developed with a solution containing 2 gms. of sodiumcarbonate, 2.5 gms. borax, 3 gms. thiourea, 4 gms. sodium sulphate, 0.4gm. phloroglucinol, 0.4 gm. resorcinol and 0.03 gm. saponin in cc.water. The copies have dark black lines, slightly tinged with red, on awhite background. They do not run and they have high contrast. Thecoupling speed of the diazonium chloride zinc chloride double salt usedis so high that the azo dye can be developed even with a neutral toslightly acid developer (pH 7-6.5) to give sufiiciently thoroughdevelopment. For example, black copies with a blueish tinge are obtainedwith a neutral developer containing 10 gms. tertiary sodium citrate, 5gms. sodium benzoate, 5 gms. anhydrous sodium acetate, 0.7 gm.phloroglucinol, 0.03 gm. acetoacetic anilide and 0.03 gm. saponinedissolved in water to 100 cc.

The diazo compound of Formula 1 is produced either by nitrosating Nethyl N (fi-phenoxy-ethyD-aniline (Clemo and Perkin, Journal of theChemical Society 121 (1922), 645) reducing the nitroso compound and 0diazotizing the reduction product or by reducing the azo dyestutfobtained from the above-mentioned N-tertiary aniline by the coupling ondiazotized sulphanilic acid and then diazotizing in known manner.

For example, 52 gms. N-ethyl-N-(B-phenoxyethyD- aniline are suspended in520 cc. of sulphuric acid and nitrosated with 40 cc. of 33% sodiumnitrite solution. The nitroso compound is reduced by the introduction ofzinc dust at 25-30 C. The resulting sulphuric acid solution is mixedwith 150 gms. ice and diazotized with 35 cc. of 33% sodium nitritesolution. The diazo compound first comes out as an oil. 60 gms. sodiumchloride are added and the reaction mixture is stirred until the zincchloride double salt appears in the form of crystals which are filteredoff with vacuum. The raw product is purified by dissolving in 1500 cc.water at 50 C., filtering over animal charcoal and separating out thezinc chloride double salt by adding 140 gms. sodium chloride.

Example II 1.7 gms. of the zinc chloride double salt of N-ethyl- N (Bphenyl mercapto ethyl) p phenylene diamine-diazonium chloride (Formula2) is dissolved in water with 0.5 gm. tartaric acid, 0.5 gm. aluminumsulphate and 6.0 gms. 1:3:6-naphthalene trisulphonic acid sodium saltand made up to 100 cc. Paper is coated in known manner with thissolution and exposed under an original after drying. Development of theexposed paper is carried out with the alkaline developer described inExample 1. Copies are obtained with very strong deep black images withno tendency to run. The

contrast is even better than with the copies obtained in the mannerdescribed in Example I, and the shade is rather more neutral, so thatthe half-tones showvas pure blacks in the copies.

Equally goodresults are obtained by using for producing thelight-sensitive layer the zinc chloride double salts of the diazoniumsalts of other paraphenylene diamine derivatives of the general formulastated above,

for example the diazonium chlorides of Formulae 3-12;

Boiling point of the correspending paraphenylene dlamlne C.)

1. N-eiihyl-N-lflheno xyethyll-p phehylene diaminediazonlum c lorldeCzH|N.CHzCH:OCtHt NzCl 2. N -ethyl-N-(fi-phenylercapto-ethyl)-pphenylene diamiue diazonlum chloride CS IILCHlGHISCIHI 3. N-ethyl--[fi-(p-chlor)- henoxyethyl1-p-phenylene 258-260 at 15 diamlne-diazoniumeh oride mm,

CSHLNiCHA-O NaGl.

Boiling point of the corresponding paraphenylene dlamine C.)

4. N-ethyl-N-[fl-(2:4-dichlor)-phenoxyethyl]-p-pheuylenediamipediazonium chloride (2-methoxy)- phenoxye thylI-p-phenyleuedlamlne-diazonium chloride 6, N-ethyl-N-[B-naphthoxy(a)-etliyl]-p-phenylcne.

dlamine-diazonium chloride campfire-8 7; N-meth minel-N-[B-phenoxyethyH-p-phenylene diazonlum chloride NEG] 8.N-propyl-N-Ifl-ghfggxyethyll-p-phenylene dtaminediazonium ch nzene oniumcram-0mm ,v The diazo compound is used in the form of thesta'nnicchloride double salt.

Boiling point of the corresponding paraphenylene diamine C.)

10. N-[d-phenoxyethyllpphenylene diamine-diaz o- 208-213" at 16 mumchloride mm.

lELN'LCz tll) NzCl 11.N-ethyl-N-[B-phenyl-snlphonyl-ethyH-p-phenylcannot be disenediamine-diazonium chloride tilled without decomposition. C2 s.N.G:H4.SO2

12. N-ethyl-N-(y-phenoxypropyl)-p-phenylene-dla- 2243-228 at 1mine-diazonium chloride mm.

CI fi-lf-O mCHI-CHL? To produce N ethyl N(fi phenyl sulphonylethyl) pphenylene diamine, phenyl B chlorethyl sulphone is reacted with ethylaniline in the presence of copper at 120 C. The reaction product is thentreated according to the instructions in Example 1.

Having now particularly described the invention, what we claim is:

1. Light sensitive diazotype material for development by the semi-wetprocess comprising a base material coated with a light-sensitive layerincluding a diazo compound of a para-phenylene diamine of the generalformula:

Ph is a phenylene radical X is selected from the group consisting of O,S and S0 R is selected from the group consisting of H and alkyl radicalshaving 1 to 3 carbon atoms R is an aromatic radical directly attached toX by a carbon atom of the aromatic ring n is selected from the groupconsisting of 2 and 3 2. Lightsensitive diazotype material fordevelopment by the semi-wet process comprising a base material coatedwith a light-sensitive layer including a diazo compound of apara-phenylene diamine of the general formula:

HzN-Ph-N 2),-XRa wherein Ph is a phenylene radical substituted by asubstituent selected from the group consisting of alkyl groups andalkoxy groups X is selected from the group consisting of O, S and S0 Ris selected from the group consisting of Hand alkyl radicals having 1 to3 carbon atoms R is an aromatic radical directly attached to X by acarbon atom of the aromatic ring n is selected from the group consistingof 2 and 3 3. Light sensitive diazotype material for development by thesemi-Wet process comprising a base material coated with a lightsensitive layer including a diazo compound of a para-phenylene diamineof the general formula:

4. Light sensitive diazotype material for development by the semi-wetprocess comprising a base material coated with a light-sensitive layerincluding a diazo compound of a para-phenylene diamine of the generalformula:

Ph is a phenylene radical X is selected from the group consisting of O,S and S0 R is selected from the group consisting of H and alkyl radicalshaving 1 to 3 carbon atoms R is an aromatic radical directly attached toX by a carbon atom of the aromatic ring and substituted by a substituentselected from the group consisting of halide atoms, alkyl groups andalkoxy groups n is selected from the group consisting of 2 and 3 5.Light sensitive diazotype material for development by the semi-wetprocess comprising a base material coated with a light-sensitive layerincluding a diazo compound of a para-phenylene diamine of the generalformula:

HzN-Ph-N 0 H2) n 2 wherein Ph is a phenylene radical X is selected fromthe group consisting of O, S and 50;;

R is selected from the group consisting of H and alkyl radicals having 1to 3 carbon atoms R is an aromatic radical directly attached to X by acarbon atom of the aromatic ring and substituted by halogen atoms n isselected from the group consisting of 2 and 3 6. Light sensitivediazotype material for development by the semi-wet process comprising abase material coated with a light-sensitive layer including a stabilizerand a diazo compound of a para-phenylene diamine of the general formula:

Phis :a phenylene radical X is selected from the group CHSlStiI1g' Of 0,S and SO,

R is selected 'from 'the group consisting *of H and alkyl radicalshaving 1 to 3 carbon atoms R, is an aromatic radical directly attachedtoX by a carbon atom of the aromatic .ring n is selected from the [groupconsisting .of 2 and 3 7. .Light. sensitive diazotype material vfordevelopment by thesemi-wet process comprising a base material coatedwith a light-sensitive layer including an anti-yellowing material and adiazo compoundof a para-phenylene diamine of the general formula:

.Ph isa phenyleneradical.

Xris selected from thergroup consisting-0f O, .S and 80;;

R is selected from the group consisting of H and alkyl radicals having 1to? carbon iatoms R, istan aromatic radical directly attachedlto X by acarbon atom of the aromatic ring n is selected from the "groupconsisting of 2'and 3 8. Lightsensitivediazotypematerial comprisingabase material coated with a light-sensitivelayer including N- ethylsNsfpphenoxyethyl) -p-phenylene diamine-diazonium chloride. l

9. Light sensitive diazotype material comprising a base material coatedwith a light sensitive layer including N- ethyl-N (fl-phenyl-merc apto-ethyl -p-phenylene diamine- References Cited in the file of thispatent UNITED STATES PATENTS 2,542,566 Pedlow et a1 Feb. 20, 19512,551,133 Jennings et a1. May 1, 1951' FOREIGN PATENTS 507,153 GreatBritain June 9, 1939 831,804 Germany Feb. 18, 1952

1. LIGHT SENSITIVE DIAZOTYPE MATERIAL FOR DEVELOPMENT BY THE SEMI-WETPROCESS COMPRISING A BASE MATERIAL COATED WITH A LIGHT-SENSITIVE LAYERINCLUDING A DIAZO COMPOUND OF A PARA-PHENYLENE DIAMINE OF THE GENERALFORMULA: